JP6106272B2 - Efficiency improved energy recovery type ventilation core - Google Patents

Description

  The present disclosure relates to a rigid or semi-rigid frame for use in an energy recovery ventilation core unit. In particular, the present disclosure relates to applying a frame bonded with a moisture permeable membrane made of a sulfonated block copolymer to provide more direct contact between the air flow and the membrane. The sulfonated block copolymer comprises at least one polymer end block comprising at least two polymer end blocks with little or no sulfonic acid functionality or sulfonate functionality and an effective amount of sulfonic acid functionality or sulfonate functionality. And have. The frame can be a porous sheet that allows the passage of a gas, such as air, thereby providing further direct contact with the moisture permeable membrane. Furthermore, the present disclosure relates to an efficiency-enhancing energy recovery type ventilation unit having a core using such a frame.

  It is well known that air conditioning systems are used to regulate the temperature of buildings and various homes. Within such a system, fresh air is introduced from outside the building or house, and indoor fresh air is exhausted outdoors. Generally, such an air conditioning system consumes a large amount of energy. One way to save this cost of energy consumption is by partially exchanging heat and moisture between the air streams as they enter and exit the structure.

  Accordingly, such systems for exchanging heat and moisture in an air stream are becoming known as energy recovery ventilation (ERV) systems. ERV involves the exchange of sensible heat and latent heat of the internal exhaust air with fresh outdoor air. The principle of such exchange is that the flow of exhaust air and the flow of intake air have different water vapor pressures, and further differ in temperature. For example, if the summer intake air flow is warm and humid, energy is recovered by exchanging both sensible heat and latent heat with cold, low-humidity exhaust air. Or, if the winter outdoor air is cold and dry, it is dry and energy is recovered by replacing the cold air with warmer and humid exhaust air.

  An ERV system is typically used in conjunction with a heating and / or cooling system and is comprised of a device having an ERV core unit. The core unit is generally composed of various laminated membranes separated by some type of spacer. The intake air flow and the exhaust air flow are generally transported to the core unit in an alternating cross flow pattern without passing through each other on each side of the laminated plate, and pass by each other. In general, sensible heat exchange is easier because heat can be transferred much more easily with a thin layer. On the other hand, the transfer of latent heat is effected by changes in humidity between air streams, resulting in a more effective heat exchange. Heat recovery ventilation (HRV) refers to a system that provides sensible heat exchange because there is no moisture exchange between both the intake air flow and the exhaust air flow. However, the ERV system is provided with a membrane that allows the movement of moisture between the two air streams, and therefore utilizes both sensible and latent heat exchange characteristics.

  An example of an ERV system is disclosed in US Patent Publication No. 2012/0073791. It discloses a core of an energy recovery system that uses a fibrous microporous support substrate and a sulfonated block copolymer laminated to the top surface. This sulfonated block copolymer does not allow air to pass but allows efficient water vapor transport, thus providing very favorable heat exchange properties. The microporous support allows for the passage of air and also provides mechanical support for the sulfonated block copolymer. Spacers are used to allow membrane lamination and air flow separation in the formation of the ERV core.

  As the inventors have identified herein, what is needed is more of an air flow and a moisture permeable membrane for more efficient moisture transfer between the intake and exhaust streams. A way for many contacts.

US Patent Application Publication No. 2012/0073791

In some embodiments, an energy recovery system having a core unit that allows heat and moisture exchange between airflows passing therethrough, the core unit comprising two or more multilayer composites. The multilayer composite structure has a structure,
A porous rigid or semi-rigid frame having a plurality of holes leading from the first surface to the second surface; and the plurality of holes joined to at least one of the first and second surfaces of the frame A polymer membrane comprising a sulfonated block copolymer covering
The sulfonated block copolymer has at least one end block A and at least one internal block B, wherein each A block contains essentially sulfonic acid functional groups or sulfonic acid ester functional groups. Instead, each B block discloses an energy recovery system that is a polymer block containing from about 10 to about 100 mole percent sulfonic acid functional groups or sulfonic acid ester functional groups based on the number of monomer units.

  In a further embodiment, the membrane is bonded onto a porous substrate comprising a porous woven or non-woven material and then bonded to at least one of the first and second surfaces of the frame. A multilayer structure is formed.

  In further embodiments, the frame may be a planar sheet or may be thermally, mechanically or chemically formed in a continuous shape with channels formed in the surface, the channels being the top and Has a bottom. In such embodiments where the frame is formed into a shape with a channel (eg, a waveform), such a frame can be used to convert an HRV system to an ERV system. This can be done by removing the plate or spacer from the HRV system and incorporating a multilayer structure with the molded (ie rigid and corrugated) frame.

  Further, the frame may have pores formed therein by drilling or sintering.

  In embodiments where the frame or multilayer structure is a planar sheet, a spacer that is itself porous and laminated with a sulfonated block copolymer on the top surface may be used.

1a, 1b and 1c show three different extruded polymer mesh frames. Figures 2a, 2b, 2c show three different perforated aluminum plates. A nonwoven cellulosic substrate is shown. 1 shows a sintered porous substrate. The perspective view of an ERV core unit is shown. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. 3 illustrates one embodiment of a layer configuration within an ERV core. The adjacent crimping frame layer is shown. The adjacent crimping frame layer is shown. The experimental result about energy exchange is shown.

  Detailed descriptions of embodiments of the present invention are disclosed herein. However, it is understood that the disclosed embodiments are merely exemplary, and that the present invention can be embodied in various alternative forms of the disclosed embodiments. Accordingly, the specific details of structures and functions featured in the embodiments disclosed herein are not intended to be limiting, but merely as a basis for claims and for those skilled in the art to use the present invention in various ways. It should be interpreted as a representative basis for teaching.

  All publications, patent applications and patents mentioned herein are incorporated in their entirety by reference. In case of conflict, the present specification (definitions, etc.) is intended to be controlled.

  Unless otherwise noted, all terminology used herein has the meaning commonly understood by one of ordinary skill in the art.

  Further, unless stated otherwise, the following expressions shall be understood to have the following meanings as used herein.

  Unless otherwise stated, the expression “coated” or “coating” means the application or bonding of a polymer in solution or liquid form to a substrate or other substance, where the polymer is Either present on the surface or embedded within the substrate structure.

  In contrast to “coated”, unless otherwise stated, the expression “laminate” refers to the application or bonding of a cast polymer membrane or polymer film to a substrate or other material.

  The term “joined” or “join” refers to the attachment of a polymer to a substrate or other material, either by coating or laminating or other means, between the polymer membrane and the substrate or other material. Including attachment to which a bond is formed.

  One skilled in the art will appreciate that the term “disclosed” membranes herein may also refer to a membrane that is moisture permeable but air impermeable.

  Disclosed herein is an improved ERV system for the exchange of sensible heat and latent heat between an intake air flow and an exhaust air flow (hereinafter “air flow” Both inhalation and exhaust flow.) For ERV systems, a moisture permeable but air impermeable membrane is used with a rigid or semi-rigid frame, which allows more contact of air flow within the ERV core. The frame may be formed in a shape such as a corrugated shape. It can be porous. The moisture permeable membrane can be bonded to the frame as well as the support substrate.

  In further embodiments, the membrane can be joined to a rigid or semi-rigid frame to form a multilayer structure, which can be formed into various shapes, such as corrugated patterns. Such embodiments may also include converting HRV units to ERV units. In such a case, a moisture impermeable spacer or frame of HRV is removed and the multilayer moisture permeable but air impermeable multilayer structure, alternatively, the porous and rigid disclosed herein. Alternatively, a semi-rigid frame can be incorporated to form an ERV core.

  In various embodiments, the ERV core disclosed herein comprises several components, such as (1) a sulfonated block copolymer membrane, (2) a rigid or semi-rigid frame, (3) a membrane substrate, (4) It may include a spacer.

Energy Recovering Ventilation Components Sulfonated Block Copolymer Membranes Polymer membranes for use in the ERV units disclosed herein are composed of or include sulfonated block copolymers. In some embodiments, compositions of the present disclosure include sulfonated block copolymers described in US 7,737,224 to Willis et al. Furthermore, sulfonated block copolymers such as those described in US 7,737,224 may be prepared according to the method of WO 2008/089332 to Dado et al. Or the method of US 8,012,539 to Handlin et al.

1. Sulfonated block copolymers The block copolymers required to prepare the sulfonated block copolymers can be obtained in several different ways, such as anionic polymerization, decelerated anionic polymerization, cationic polymerization, Ziegler-Natta polymerization, and living chain or stable free radicals. It can be made by polymerization. Anionic polymerization is described in more detail below and is also described in the references. Decelerated anionic polymerization methods for making styrenic block copolymers are, for example, US 6,391,981, US 6,455,651 and US 6,492,469, each of which is incorporated herein by reference. Is disclosed. Cationic polymerization methods for preparing block copolymers are disclosed, for example, in US 6,515,083 and US 4,946,899, each incorporated herein by reference.

  Living Ziegler-Natta polymerization methods that can be used to make block copolymers have recently been described by W. Coates, P.A. D. Hustad, and S.M. Reinartz, Angew. Chem. Int. Ed. , 41, 2366-2257 (2002), a review article is presented. Zhang and K.K. A subsequent publication by Nomura (J. Am. Chem. Soc., Comm., 2005) specifically describes the Living Ziegler-Natta technique for making styrenic block copolymers. Extensive research in the field of nitroxide-mediated living radical polymerization chemistry provides a review. C. J. et al. Hawker, A .; W. Bosman, and E.M. Harth, Chem. Rev. , 101 (12), 3661-3688 (2001). As outlined in this review, styrenic block copolymers can be synthesized by living or stable free radical techniques. The nitroxide mediated polymerization method is a preferred living chain or stable free radical polymerization method when preparing precursor polymers.

2. Polymer Structure One aspect of the present disclosure relates to the polymer structure of a sulfonated block copolymer. In one embodiment, the neutralized block copolymer has at least two polymer ends or outer blocks A and at least one saturated polymer inner block B, wherein each A block is resistant to sulfonation. Each B block is a polymer block that is easily sulfonated.

  Preferred block copolymer structures have the general configurations ABA, (AB) n (A), (ABA) n, (ABA) nX, (AB) nX, A -B-D-B-A, A-D-B-D-A, (A-D-B) n (A), (A-B-D) n (A), (A-B-D) nX, (A-D-B) nX or mixtures thereof, where n is an integer from 2 to about 30, X is the residue of the coupling agent, and A, B and D are In the present specification, it is defined as follows.

  The most preferred structures are linear structures such as ABA, (AB) 2X, ABDBA, (ABDD) 2X, ADB. -D-A, and (A-D-B) 2X and radial structures such as (A-B) nX and (A-D-B) nX (where n is 3 to 6). is there. Such block copolymers are typically made by anionic polymerization, stable free radical polymerization, cationic polymerization or Ziegler-Natta polymerization. Preferably, the block copolymer is made by anionic polymerization. One skilled in the art will appreciate that in any polymerization, the polymer mixture will include a certain amount of AB diblock copolymer in addition to the linear and / or radial polymer (any). Each amount has not been found to be harmful.

  The A block consists of polymerized (i) para-substituted styrene monomer, (ii) ethylene, (iii) α-olefin of 3 to 18 carbon atoms, (iv) 1,3-cyclodiene monomer, (v) hydrogen One or more segments selected from monomers of conjugated dienes having a vinyl content of less than 35 mole percent prior to conversion, (vi) acrylic acid esters, (vii) methacrylic acid esters, and (viii) this mixture. When the A segment is a polymer of 1,3-cyclodiene or conjugated diene, the segment is hydrogenated after polymerization of the block copolymer and before sulfonation of the block copolymer.

  Para-substituted styrene monomers include para-methyl styrene, para-ethyl styrene, para-n-propyl styrene, para-iso-propyl styrene, para-n-butyl styrene, para-sec-butyl styrene, para-iso-butyl. Selected from styrene, para-t-butylstyrene, para-decylstyrene isomer, para-dodecylstyrene isomer and mixtures of the above monomers. Preferred para-substituted styrene monomers are para-t-butyl styrene and para-methyl styrene, with para-t-butyl styrene being most preferred. The monomer may be a monomer mixture, depending on the specific source. Desirably, the total purity of the para-substituted styrene monomer is at least 90%, preferably at least 95%, and even more preferably at least 98% by weight of the desired para-substituted styrene monomer.

  When the A block is a polymer segment of ethylene, W. It may be useful to polymerize ethylene by the Ziegler-Natta method as taught in the review of references by Coates et al (the disclosure of which is incorporated herein by reference). The ethylene block is preferably made using an anionic polymerization technique as taught in US 3,450,795, the disclosure of which is incorporated herein by reference. The block molecular weight of such ethylene blocks is typically from about 1,000 to about 60,000.

  When the A block is a polymer of alpha olefins of 3 to 18 carbon atoms, such polymers are W. Prepared by the Ziegler-Natta method as taught in the above review of the reference by Coates et al., Preferably the α-olefin is propylene, butylene, hexane or octane, with propylene being most preferred. The block molecular weight of each such α-olefin block is typically from about 1,000 to about 60,000.

  When the A block is a hydrogenated polymer of 1,3-cyclodiene monomer, such monomer is selected from the group consisting of 1,3-cyclohexadiene, 1,3-cycloheptadiene and 1,3-cyclooctadiene. The Preferably, the cyclodiene monomer is 1,3-cyclohexadiene. The polymerization of such cyclodiene monomers is disclosed in US 6,699,941, the disclosure of which is hereby incorporated by reference. When a cyclodiene monomer is used, it is necessary to hydrogenate the A block because a polymerized cyclodiene block that is not hydrogenated is easily sulfonated. Thus, after synthesis of the A block using 1,3-cyclodiene monomer, the block copolymer is hydrogenated.

  When the A block is a hydrogenated polymer of an acyclic conjugated diene having a vinyl content of less than 35 mole percent prior to hydrogenation, the conjugated diene is preferably 1,3-butadiene. The vinyl content of the polymer prior to hydrogenation should be less than 35 mole percent, preferably less than 30 mole percent. In some specific embodiments, the vinyl content of the polymer prior to hydrogenation is less than 25 mole percent, even more preferably less than 20 mole percent, even less than 15 mole percent, which is more convenient for the polymer before hydrogenation. An example of such a vinyl content is less than 10 mole percent. Thus, A block has the same crystalline structure as polyethylene. The structure of such an A block is disclosed in US Pat. No. 3,670,054 and US Pat. No. 4,107,236, the disclosures of each of which are incorporated herein by reference.

  The A block may be a polymer segment of acrylic ester or methacrylic ester. Such polymer blocks can be made according to the methods disclosed in US Pat. No. 6,767,976, the disclosure of which is incorporated herein by reference. Specific examples of methacrylic acid esters include esters of primary alcohol and methacrylic acid, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl. Methacrylate, methoxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, trimethoxysilylpropyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl methacrylate, secondary alcohol and methacrylic acid esters such as isopropyl methacrylate, cyclohexyl Methacrylate and A Isobornyl methacrylate and esters of a tertiary alcohol and methacrylic acid, for example, tert- butyl methacrylate. Specific examples of acrylic esters include esters of primary alcohol and acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, lauryl. Acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, glycidyl acrylate, trimethoxysilylpropyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, secondary alcohol and acrylic acid ester such as isopropyl acrylate, cyclohexyl Acrylate and isobornyl acrylate, and tertiary al Esters Lumpur acrylic acid, for example, tert- butyl acrylate. If necessary, one or more other anionic polymerizable monomers may be used together with the (meth) acrylic acid ester as a raw material (one or more). Examples of anionic polymerizable monomers that may optionally be used include methacrylic or acrylic monomers such as trimethylsilyl methacrylate, N-, N-dimethylmethacrylamide, N, N-diisopropylmethacrylamide, N, N-diethylmethacrylamide N, N-methylethylmethacrylamide, N, N-di-tert-butylmethacrylamide, trimethylsilyl acrylate, N, N-dimethylacrylamide, N, N-diisopropylacrylamide, N, N-methylethylacrylamide and N , N-di-tert-butylacrylamide. Further, two or more methacrylic or acrylic structures in the molecule, such as a methacrylic ester structure or an acrylic ester structure (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1 , 4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate) May be.

  In the polymerization method used for preparing the polymer block of acrylic ester or methacrylic ester, only one type of monomer (for example, (meth) acrylic ester) may be used, or two or more types are used in combination. May be. When two or more kinds of monomers are used in combination, any copolymerization form selected from copolymerization forms such as random, block, tapered block, etc. can be used under conditions such as the combination of monomers and the timing of adding the monomer to the polymerization system. (E.g., simultaneous addition of two or more monomers, or separate additions at given time intervals) can be performed.

  The A block may also include up to 15 mole percent aromatic vinyl monomers, such as those present in the B block, which will be discussed in more detail below. In some embodiments, the A block may contain up to 10 mole percent of the aromatic vinyl monomer described for the B block, preferably only up to 5 mole percent, particularly preferably up to 2 mole percent. Is. However, in the most preferred embodiment, the A block does not contain vinyl monomers present in the B block. The sulfonation level of the A block can be from 0 to 15 mole percent of all monomers in the A block. Those skilled in the art will appreciate that suitable ranges include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein.

  The B block is in each case an unsubstituted styrene monomer, an ortho-substituted styrene monomer, a meta-substituted styrene monomer, an α-methylstyrene monomer, a 1,1-diphenylethylene monomer, a 1,2-diphenylethylene monomer, and mixtures thereof It includes a segment of one or more types of polymerized aromatic vinyl monomers selected from: Also, in addition to the monomers and polymers described above, the B block has a vinyl content of 20 to 80 mole percent selected from such monomer (s) and 1,3-butadiene, isoprene and mixtures thereof. It may include partially or fully hydrogenated copolymers with conjugated dienes. Such copolymers with partially or fully hydrogenated dienes can be random copolymers, tapered copolymers, block copolymers or distribution controlled copolymers. In one preferred embodiment, the B block is selectively partially or fully hydrogenated and comprises a copolymer of a conjugated diene and an aromatic vinyl monomer described in this paragraph. In another preferred embodiment, the B block is an unsubstituted styrene monomer block, which is saturated due to the nature of the monomer and does not require additional processing steps to hydrogenate. B blocks having a distribution-controlled structure are disclosed in US 7,169,848, the disclosure of which is incorporated herein by reference. US 7,169,848 also discloses the preparation of sulfonated block copolymers. B blocks containing styrene blocks are described herein. In one preferred embodiment, the B block is composed of unsubstituted styrene and does not require a separate hydrogenation step.

  In another aspect of the present disclosure, the block copolymer comprises at least one impact modifier block D having a glass transition temperature below 20 ° C. In one embodiment, impact modifier block D comprises a hydrogenated polymer or copolymer of conjugated dienes selected from isoprene, 1,3-butadiene and mixtures thereof, wherein the butadiene portion of the polymer block is 20 The polymer block has a number average molecular weight of 1,000 to 50,000. In another embodiment, the impact modifier block D comprises an acrylate polymer or silicone polymer having a number average molecular weight of 1,000 to 50,000. In yet another embodiment, the impact modifier block D block is a polymer block of isobutylene having a number average molecular weight of 1,000 to 50,000.

  Each A block independently has a number average molecular weight of about 1,000 to about 60,000, and each B block independently has a number average molecular weight of about 10,000 to about 300,000. Preferably, each A block has a number average molecular weight of 2,000 to 50,000, more preferably 3,000 to 40,000, and even more preferably 3,000 to 30,000. Preferably, each B block has a number average molecular weight of 15,000 to 250,000, more preferably 20,000 to 200,000, and even more preferably 30,000 to 100,000. Those skilled in the art will appreciate that suitable ranges include any combination of the specified number average molecular weights, even if specific combinations and ranges are not listed herein. . Such molecular weight is most accurately measured by light scattering measurement and is displayed as a number average molecular weight. Preferably, the sulfonated polymer is from about 8 mole percent to about 80 mole percent, preferably from about 10 to about 60 mole percent A block, more preferably more than 15 mole percent A block, even more preferably about 20 mole percent. To about 50 mole percent A block.

  Aromatic vinyl monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, α-methylstyrene monomers, 1,1-diphenylethylene monomers and 1,2-diphenylethylene monomers in sulfonated block copolymers The relative amount of is from about 5 to about 90 mole percent, preferably from about 5 to about 85 mole percent. In alternative embodiments, the amount is from about 10 to about 80 mole percent, preferably from about 10 to about 75 mole percent, more preferably from about 15 to about 75 mole percent, and most preferably from about 25 to about 75 mole percent. 70 mole percent. Those skilled in the art will appreciate that the preferred range encompasses any combination of the stated mole percentages, even if the specific combination is not listed herein.

  In a preferred embodiment, in each B block, an unsubstituted styrene monomer, an ortho-substituted styrene monomer, a meta-substituted styrene monomer, an α-methylstyrene monomer, a 1,1-diphenylethylene monomer, and a 1,2-diphenylethylene monomer. The mole percent of certain aromatic vinyl monomers is from about 10 to about 100 mole percent, preferably from about 25 to about 100 mole percent, more preferably from about 50 to about 100 mole percent, even more preferably from about 75 to about 100 mole percent, Most preferred is 100 mole percent. Those skilled in the art will appreciate that suitable ranges include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein.

  A typical sulfonation level is such that each B block contains one or more sulfonic acid functional groups. Preferred sulfonation levels are unsubstituted styrene monomer, ortho-substituted styrene monomer, meta-substituted styrene monomer, α-methylstyrene monomer, 1,1-diphenylethylene monomer and 1,2-diphenylethylene monomer in each B block. 10 to 100 mole percent, more preferably about 20 to 95 mole percent, and even more preferably about 30 to 90 mole percent, relative to the mole percent of certain aromatic vinyl monomers. Those skilled in the art will appreciate that suitable ranges for sulfonation include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein. Let's be done. The sulfonation level is measured by titration of a dry polymer sample (which is redissolved in tetrahydrofuran) using a standard solution containing NaOH in a mixed solvent of alcohol and water.

3. General Anionic Method for Preparing Polymers Anionic polymerization methods involve polymerizing a suitable monomer in solution with a lithium initiator. The solvent used as the polymerization medium is any hydrocarbon that does not react with the living anionic chain ends of the polymer being formed, is easy to handle in commercially available polymerization units, and provides suitable solubility characteristics for the product polymer. possible. For example, nonpolar aliphatic hydrocarbons (which generally have no ionizable hydrogen atoms) are particularly suitable solvents. Often used are cyclic alkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, which are all relatively nonpolar. Other suitable solvents are known to those skilled in the art and can be selected to perform effectively in a given set of processing conditions, with the polymerization temperature being one of the major factors considered.

  Starting materials for preparing the block copolymers of the present disclosure include the initial monomers described above. Other important starting materials for anionic copolymerization include one or more polymerization initiators. In the present disclosure, suitable initiators include, for example, alkyl lithium compounds such as s-butyl lithium, n-butyl lithium, t-butyl lithium, amyl lithium, and other organolithium compounds such as di-type. Initiators, for example, di-sec-butyllithium adducts of m-diisopropenylbenzene. Other such di-type initiators are disclosed in US 6,492,469, the disclosure of which is incorporated herein by reference. Of various polymerization initiators, s-butyllithium is preferred. The initiator can be used in the polymerization mixture (including monomer and solvent) in an amount calculated on the basis of one molecule of initiator per desired polymer chain. Lithium initiator processes are well known and are described, for example, in US Pat. No. 4,039,593 and US Reissued Patent No. 27,145, the disclosures of each of which are incorporated herein by reference. .

  The polymerization conditions for preparing the block copolymers of the present disclosure are typically similar to those used for anionic polymerization in general. The polymerization is preferably carried out at a temperature of from about -30 ° C to about 150 ° C, more preferably from about 10 ° C to about 100 ° C, most preferably from about 30 ° C to about 90 ° C in view of industrial limitations. The polymerization is performed in an inert atmosphere, preferably under nitrogen, and may be performed under a pressure in the range of about 0.5 to about 10 bar. This copolymerization generally requires less than about 12 hours and can be performed in about 5 minutes to about 5 hours, depending on the temperature, the concentration of monomer components and the desired molecular weight of the polymer. When two or more types of monomers are used in combination, any copolymerized form selected from copolymerized forms such as random, block, tapered block, and distribution control type block can be used.

One skilled in the art will appreciate that the anionic polymerization process can be slowed by the addition of Lewis acids such as alkylaluminum, alkylmagnesium, alkylzinc or combinations thereof. The effect of the addition of Lewis acid to the polymerization method is
1) The viscosity of the living polymer solution is reduced, allowing a method to be operated at a high polymer concentration, thus using less solvent,
2) The thermal stability of the living polymer chain ends is improved, which enables polymerization at high temperatures, which also reduces the viscosity of the polymer solution and reduces the use of solvents, and 3) The reaction rate is slow, which allows polymerization at higher temperatures while using the same technique for heat removal of reactions used in standard anionic polymerization methods.

  The process benefits of using Lewis acids to slow anionic polymerization techniques are described in US 6,391,981, US 6,455,651 and US 6,492,469, the disclosures of each of which are incorporated herein by reference. Is disclosed. Related information is disclosed in US 6,444,767 and US 6,686,423, the disclosures of each of which are incorporated herein by reference. Polymers that can be made by such a slow anionic polymerization method can have the same structure as those prepared using conventional anionic polymerization methods, and thus this method is useful for making the polymers of the present disclosure. It can be. In the decelerating anionic polymerization method with Lewis acid, a reaction temperature of 100 ° C. to 150 ° C. is preferred because it is possible to use the reaction at a very high polymer concentration at this temperature. Although a stoichiometric excess of Lewis acid may be used, in most cases there will not be enough benefit to convince the additional cost of excess Lewis acid in improving the process. In order to obtain improvements in the performance of the process using the slow anionic polymerization technique, it is preferred to use from about 0.1 to about 1 mole of Lewis acid per mole of living anion chain ends.

  Preparation of radial (branched) polymers requires a post-polymerization step called “coupling”. In the radial form described above, n is an integer from 3 to about 30, preferably from about 3 to about 15, more preferably from 3 to 6, and X is the remainder or residue of the coupling agent. Various coupling agents are known in the art and can be used to prepare the block copolymers. Such include, for example, dihaloalkanes, silicon halides, siloxanes, polyfunctional epoxides, silica compounds, esters of monohydric alcohols and carboxylic acids (eg, methyl benzoate and dimethyl adipate) and epoxidized oils. It is done. Star shaped polymers are disclosed, for example, in US 3,985,830, US 4,391,949 and US 4,444,953, and CA 716,645, the disclosure of each of which is incorporated herein by reference. It is prepared using a polyalkenyl coupling agent. Suitable polyalkenyl coupling agents include divinylbenzene, preferably m-divinylbenzene. Preference is given to tetra-alkoxysilanes such as tetra-methoxysilane (TMOS) and tetra-ethoxysilane (TEOS), tri-alkoxysilanes such as methyltrimethoxysilane (MTMS), aliphatic diesters such as dimethyl adipate And diethyl adipate, and diglycidyl aromatic epoxy compounds such as diglycidyl ethers derived from the reaction of bis-phenol A with epichlorohydrin.

  Linear polymers can also be prepared by a “coupling” step after polymerization. However, unlike radial polymers, “n” in the above formula is the integer 2 and X is the remainder or residue of the coupling agent.

4). Methods for preparing hydrogenated block copolymers As described, in some cases (1) when a diene is present in the B internal block, (2) a polymer in which the A block is 1,3-cyclodiene If (3) the impact modifier block D is present, and (4) the A block is a polymer of a conjugated diene having a vinyl content of less than 35 mole percent, a block copolymer is selected. It is necessary to hydrogenate and to remove any ethylenic unsaturation prior to sulfonation. Hydrogenation generally improves thermal stability, ultraviolet light stability, oxidative stability, thus improving the weather resistance of the final polymer and reducing the risk of sulfonation of the A block or D block.

  Hydrogenation can be carried out by any of several hydrogenation methods or selective hydrogenation methods known in the prior art. Such hydrogenation is described, for example, in US Pat. No. 3,595,942, US Pat. No. 3,634,549, US Pat. No. 3,670,054, US Pat. No. 3,700,633, and US Pat. Incorporated in the specification)) and the like. These processes are based on the action of a suitable catalyst, operated so that the polymer containing ethylenic unsaturation is hydrogenated. Such catalysts or catalyst precursors are preferably those containing a Group 8 to 10 metal, such as nickel or cobalt, and suitable reducing agents, such as alkyl aluminum or elements 1, 2, and 13 of the periodic table of elements. Used in combination with a metal selected from the group, in particular hydrides of lithium, magnesium or aluminum. This preparation may be performed in a suitable solvent or diluent at a temperature of about 20 ° C. to about 80 ° C. Other useful catalysts include titanium-based catalyst systems.

  Hydrogenation may be performed under conditions such that at least about 90 percent of the conjugated diene double bonds are reduced and zero to 10 percent of the arene double bonds are reduced. A preferred range is one in which at least about 95 percent of the conjugated diene double bonds are reduced, more preferably about 98 percent of the conjugated diene double bonds are reduced.

  When the hydrogenation is complete, the polymer solution, together with a relatively large amount of aqueous acid (preferably 1 to 30 weight percent acid), has a volume ratio of about 0.5 parts aqueous acid to 1 part polymer solution. The catalyst is preferably oxidized and extracted by stirring at The nature of this acid is not important. Suitable acids include phosphoric acid, sulfuric acid and organic acids. This stirring is continued for about 30 to about 60 minutes at about 50 ° C. while sparging a mixture of oxygen and nitrogen. Care must be taken in this process to avoid the formation of an explosive mixture of oxygen and hydrocarbons.

5. Methods for Making Sulfonated Polymers According to many embodiments disclosed herein, the block copolymer prepared above is sulfonated to obtain a sulfonated polymer product in liquid, micellar form. In this micelle form, the sulfonated block copolymer can be neutralized before being cast on the membrane, while at the same time the sulfonated block copolymer remains liquid and the risk of gelling and / or precipitation is reduced.

  Without being bound by any particular theory, the micelle structure of the sulfonated block copolymer has a core that includes the sulfonated block (s) with a significant amount of consumed sulfonating agent residues, It is a belief in the present invention that the core is surrounded by sulfonated resistant block (s) and can be described as further swelled by organic non-halogenated aliphatic solvents. As described in more detail below, the sulfonated block is highly polar due to the presence of sulfonic acid functional groups and / or sulfonic acid ester functional groups. Accordingly, such sulfonated blocks are sequestered within the core, while the outer sulfonated resistant block forms a shell that is solvated by the non-halogenated aliphatic solvent. In addition to the formation of discrete micelles, the formation of polymer aggregates can also be seen. Without being bound by any particular theory, polymer aggregates are discrete structures, or non-discrete structures resulting from association of polymer chains in a manner other than that shown for micelles, and / or loosely aggregated Can be described as two or more discrete micelle groups. Accordingly, a solvated sulfonated block copolymer in the form of micelles may comprise discrete micelles and / or micelle aggregates, such solutions may optionally contain aggregated polymer chains having a structure other than the micelle structure. May also be included.

  Micelles can be formed as a result of the sulfonation process, or the block copolymer can be arranged in a micelle structure prior to sulfonation.

  In some embodiments, the sulfonation method described in WO2008 / 089332 can be used to form micelles. The method is useful for the preparation of sulfonated styrenic block copolymers as described in US2007 / 021569.

  After polymerization, the polymer can be sulfonated using a sulfonate reagent such as acyl sulfate in at least one non-halogenated aliphatic solvent. In some embodiments, the precursor polymer can be sulfonated after being isolated from the reaction mixture resulting from the preparation of the precursor polymer, washed and dried. In some other embodiments, the precursor polymer can be sulfonated without isolation from the reaction mixture resulting from the preparation of the precursor polymer.

(I) Solvent The organic solvent is preferably a non-halogenated aliphatic solvent, a first non-halogenated aliphatic that serves to solvate one or more sulfonated resistant blocks or non-sulfonated blocks of the copolymer It contains a solvent. The first non-halogenated aliphatic solvent can include a substituted or unsubstituted cycloaliphatic hydrocarbon having about 5 to 10 carbons. Non-limiting examples include cyclohexane, methylcyclohexane, cyclopentane, cycloheptane, cyclooctane and mixtures thereof. The most preferred solvents are cyclohexane, cyclopentane and methylcyclohexane. The first solvent may be the same solvent used as a polymerization medium for anionic polymerization of the polymer block.

  In some embodiments, the block copolymer can be in micellar form prior to sulfonation, even when using only the first solvent. By adding a second non-halogenated aliphatic solvent to the solution of the precursor polymer in the first non-halogenated aliphatic solvent, a “pre-form” of the polymer micelles and / or other polymer aggregates can be achieved. Or it can be assisted. On the other hand, the second non-halogenated solvent is preferably miscible with the first solvent but is a poor solvent within the temperature range of the process for the easily sulfonated block of the precursor polymer, and It is selected so as not to disturb the sulfonation reaction. In other words, preferably the easily sulfonated block of the precursor polymer is substantially insoluble in the second non-halogenated solvent within the temperature range of the process. When the easily sulfonated block of the precursor polymer is polystyrene, suitable solvents that are poor solvents for polystyrene and that can be used as the second non-halogenated solvent include linear and up to about 12 carbon atoms and Examples thereof include branched aliphatic hydrocarbons such as hexane, heptane, octane, 2-ethylhexane, isooctane, nonane, decane, paraffin oil, and paraffin mixed solvent. A preferred example of the second non-halogenated aliphatic solvent is n-heptane.

The pre-formation of polymer micelles and / or other polymer aggregates allows the polymer to be sulfonated at essentially higher concentrations than would be feasible without the addition of a second said solvent, with essentially no gelation ineffectiveness. It becomes possible to proceed. Moreover, this approach, the utility of high polarity acyl sulfate, for example C ₃ acyl sulfate (propionyl sulfate) may be significantly improved in terms of minimizing the sulfonation conversion and by-products of the polymer. In other words, this approach can improve the utility of highly polar sulfonation reagents. Such acyl sulfates are further described below.

(Ii) Polymer concentration According to some embodiments, a high level of styrene sulfonation is achieved by maintaining the concentration of the precursor polymer below the critical concentration of the precursor polymer, at least during the initial stages of sulfonation. The reaction mixture, reaction product or both can be performed in a manner that is substantially free of polymer precipitation and gelation is not ineffective. Those skilled in the art will appreciate that in mixtures that are substantially free of polymer precipitation, trace amounts of polymer may be deposited on the surface as a result of local solvent evaporation during the process. . For example, according to some embodiments, if less than 5% of the polymer is precipitated in the mixture, the mixture is considered substantially free of polymer precipitation.

  The polymer concentration at which sulfonation can take place depends on the composition of the starting polymer. This is because the critical concentration depends on the polymer composition, below which the gelation of the polymer is not nullified or negligible. As noted above, the critical concentration can also depend on other factors, such as the particular solvent or solvent mixture used and the desired degree of sulfonation. In general, the polymer concentration is preferably from about 1% to about 30%, or from about 1% to about 20%, or from about 1% to about 20% by weight, based on the total weight of the reaction mixture, which is preferably substantially free of halogenated solvents. It is in the range of about 1% to about 15%, or about 1% to about 12%, or about 1% to about 10% by weight. Those skilled in the art will appreciate that suitable ranges include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein.

  According to some embodiments of the described technology, the initial concentration of the precursor block polymer or precursor block polymer mixture is less than the threshold concentration of the precursor polymer (s), or the total reaction mixture From about 0.1% by weight to a concentration that is less than the critical concentration of the precursor polymer (s) or from about 0.5% by weight of the precursor polymer (s) Up to a concentration that is less than the critical concentration of, or from about 1.0 wt% to a concentration that is about 0.1 wt% below the limiting concentration of the precursor polymer (s), or from about 2.0 wt% To a concentration about 0.1% by weight below the critical concentration of the precursor polymer (s) or from about 3.0% by weight to the critical concentration of the precursor polymer (s) Maintained at a concentration of about 0.1% by weight, or from about 5.0% to a concentration of about 0.1% by weight below the critical concentration of the precursor polymer (s). Good. Those skilled in the art will appreciate that suitable ranges include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein.

  In at least some embodiments, maintaining the polymer concentration below the critical concentration can result in a reaction mixture having a low concentration of by-product carboxylic acid compared to high concentration conditions that result in gelation.

  However, those skilled in the art will recognize that the total concentration of the polymer (s) in the reaction mixture may be high when making the sulfonated polymer of some embodiments of the technology, particularly in a semi-batch or continuous production process. It will be appreciated that it may be higher than the limiting concentration of the precursor polymer.

(Iii) Sulfonating agents According to many embodiments, acyl sulfates can be used for sulfonation of polymerized block copolymers. Acyl groups, derived from a _preferably, C 2 -C ₈ or _C 3 -C ₈ or _C 3 -C ₅ linear, branched or cyclic carboxylic acid, anhydride or acid chloride, or mixtures thereof To do. Preferably, such compounds are non-aromatic carbon-carbon double bonds, hydroxyl groups, or any other functional moiety that is reactive with acyl sulfate or that is readily degraded under sulfonation reaction conditions. Is not included. For example, an acyl group having an aliphatic quaternary carbon at the α-position of the carbonyl function (eg, acyl sulfate derived from trimethylacetic anhydride) appears to be easily decomposed during the sulfonation reaction of the polymer, Preferably, it should be avoided in the described technique. Also, the range of acyl groups useful for the creation of acyl sulfates in the art includes those derived from aromatic carboxylic acids, anhydrides and acid chlorides such as benzoic anhydride and phthalic anhydride. More preferably, the acyl group is selected from the group of acetyl, propionyl, n-butyryl and isobutyryl. Even more preferably, the acyl group is isobutyryl. It has been found that isobutyryl sulfate can lead to a high degree of polymer sulfonation and the formation of by-products can be relatively minimal.

  The formation of acyl sulfate from carboxylic anhydride and sulfuric acid involves the following reaction

によって表され得る。硫酸アシルはスルホン化反応の過程で低速分解に供され、以下の式

Can be represented by: Acyl sulfate is subjected to slow decomposition during the sulfonation reaction, and the following formula

のα−スルホン化カルボン酸が形成される。

Of α-sulfonated carboxylic acid.

  In one embodiment of the described technique, an acyl sulfate reagent is obtained from carboxylic anhydride and sulfuric acid in a separate “pre-creation” reaction prior to addition to the polymer solution in a non-halogenated aliphatic solvent. . The pre-creation reaction may be performed with or without a solvent. If a solvent is used to pre-create the acyl sulfate, the solvent is preferably non-halogenated. Alternatively, the acyl sulfate reagent may be obtained in an in situ reaction in a polymer solution with a non-halogenated aliphatic solvent. According to this embodiment of the technology, the molar ratio of anhydride to sulfuric acid can be from about 0.8 to about 2, preferably from about 1.0 to about 1.4. The sulfuric acid used in this preferred process is preferably one having a concentration of about 93% to about 100%, more preferably about 95% to about 100%, by weight. Those skilled in the art can use fuming sulfuric acid as an alternative to sulfuric acid in an in situ reaction to create acyl sulfates, but the strength of fuming sulfuric acid is such that unintentional carbonization of the reaction mixture is avoided or minimized. It will be understood that it should be low enough.

  In another embodiment of the present technology, the acyl sulfate reagent may be obtained from carboxylic anhydride and fuming sulfuric acid in a separate “pre-creation” reaction, prior to addition to the polymer solution in the aliphatic solvent. In this case, the strength of fuming sulfuric acid is about 1% to about 60% sulfur trioxide free, or about 1% to about 46% sulfur trioxide free, or about 10% to about 46% sulfur trioxide free The molar ratio of anhydride to sulfuric acid present in the fuming sulfuric acid is from about 0.9 to about 1.2.

  Further, acyl sulfate reagents can be prepared from carboxylic anhydrides by reaction with any combination of sulfuric acid, fuming sulfuric acid or sulfur trioxide. Further, acyl sulfate reagents can be prepared from carboxylic acids by reaction with chlorosulfonic acid, fuming sulfuric acid, sulfur trioxide or any combination thereof. In addition, acyl sulfate reagents can also be prepared from carboxylic acid chlorides by reaction with sulfuric acid. Alternatively, acyl sulfates can be prepared from any combination of carboxylic acids, anhydrides and / or acid chlorides.

  Sulfonation of the styrenic repeating unit of the polymer with acyl sulfate is the reaction

によって表され得る。

Can be represented by:

  The acyl sulfate reagent ranges from very low levels for light sulfonated polymer products to high levels for heavy sulfonated polymer products, relative to the number of moles of easily sulfonated monomer repeat units present in the polymer solution. Can be used in any amount. The molar amount of acyl sulfate can be defined as the theoretical amount of acyl sulfate that can be created by a given method, the amount being governed by the limiting reagents in the reaction. The molar ratio of acyl sulfate to styrene repeat units (ie, easily sulfonated units) according to some embodiments of the present technology is about 0.1 to about 2.0, or about 0.2 to about 1.3, or about It can range from 0.3 to about 1.0.

  According to at least some embodiments of the described technology, the degree of sulfonation of the easily sulfonated aromatic vinyl monomer in the block polymer is about 0.4 milliequivalents of sulfonic acid per gram of sulfonated polymer ( meq) (0.4 meq / g) or more than about 0.6 meq (0.6 meq / g) sulfonic acid per gram of sulfonated polymer or sulfonic acid per gram of sulfonated polymer More than about 0.8 meq (0.8 meq / g) or more than about 1.0 meq (1.0 meq / g) sulfonic acid per gram of sulfonated polymer or sulfone per gram of sulfonated polymer The acid is greater than about 1.4 meq (1.4 meq / g). For example, after sulfonation of the above precursor polymer according to the methods of the presently described technique, a typical sulfonation level is such that each B block contains one or more sulfonic acid functional groups. Preferred sulfonation levels are from about 10 to about 100 mole percent, or from about 20 to 95 mole percent, or from about 30 to 90 mole percent, and / or relative to the mole percent of easily sulfonated aromatic vinyl monomer in each B block About 40 to about 70 mole percent, such as, for example, unsubstituted styrene monomer, ortho-substituted styrene monomer, meta-substituted styrene monomer, α-methylstyrene monomer, 1,1-diphenylethylene monomer, 1,2 -It may be a diphenylethylene monomer, a derivative thereof, or a mixture thereof. Those skilled in the art will appreciate that suitable ranges of sulfonation levels include any combination of the stated mole percentages, even if specific combinations and ranges are not listed herein. It will be understood.

The sulfonation level or degree of sulfonation of the sulfonated polymer uses NMR and / or titration methods known to those skilled in the art and / or two separate titrations that can be recognized by those skilled in the art described in the examples below. It can be measured by a method. For example, the solution obtained by the method of the present technology can be analyzed by ¹ H-NMR at about 60 ° C. (± 20 ° C.). The percentage of styrene sulfonation can be calculated by integrating the aromatic signal of the ¹ H-NMR spectrum. In another example, the reaction product measures the levels of styrenic polymer sulfonic acid, sulfuric acid, and non-polymeric by-product sulfonic acid (eg, 2-sulfo-alkyl carboxylic acid) and It can be analyzed by two separate titrations (“two-titration method”) that calculate the degree of styrene sulfonation based on it. Alternatively, the sulfonation level can also be determined by titration of a dry polymer sample (which is redissolved in tetrahydrofuran) using a standard solution containing NaOH in a mixture of alcohol and water. In the latter case, strict removal of the by-product acid is preferably ensured.

  While embodiments relating to polymer sulfonation have been described above in the context of acyl sulfate reagents, the utility of other sulfonation reagents is envisioned. For example, the use of sulfur trioxide and phosphate esters such as sulfonation reagents derived by triethyl phosphate complexation / reaction has been demonstrated in the art. The chemistry of such sulfonation reagents that results in aromatic sulfonation with a significant degree of sulfonic acid alkyl ester incorporation is known in the art. For this reason, the sulfonated polymer obtained may contain both sulfonic acid groups and sulfonic acid alkyl ester groups. Other contemplated sulfonation reagents include, but are not limited to, those derived by reaction or complexation of sulfur trioxide with phosphorus pentachloride, polyphosphoric acid, 1,4-dioxane, triethylamine, and the like.

(Iv) Reaction conditions Sulfonation reaction between acyl sulfate and an easily sulfonated block copolymer, such as an aromatic-containing polymer (eg, styrenic block copolymer) is from about 20 ° C to about 150 ° C, or from about 20 ° C to about 100 ° C. Or a reaction temperature in the range of about 20 ° C. to about 80 ° C., or about 30 ° C. to about 70 ° C., or about 40 ° C. to about 60 ° C. (eg, about 50 ° C.). The reaction time can range from less than about 1 minute to about 24 hours or more depending on the reaction temperature. In some preferred acyl sulfate embodiments using an in situ reaction of carboxylic anhydride and sulfuric acid, the initial temperature of the reaction mixture can be about the same as the target reaction temperature for sulfonation. Alternatively, the initial temperature may be lower than the target reaction temperature for subsequent sulfonation. In a preferred embodiment, the acyl sulfate can be created in situ at about 20 ° C. to about 40 ° C. (eg, about 30 ° C.) for about 0.5 to about 2 hours, or about 1 to about 1.5 hours, The reaction mixture can then be heated from about 40 ° C. to about 60 ° C. to expedite the completion of the reaction.

  Although not required, the optional reaction quenching step can be performed by the addition of a quenching agent, which can be, for example, water or a hydroxyl-containing compound, such as methanol, ethanol or isopropanol. Typically, in such a step, an amount of quenching agent sufficient to react with at least unreacted residual acyl sulfate can be added.

  In some embodiments of the described technology, sulfonation of the aromatic-containing polymer in a non-halogenated aliphatic solvent involves contacting the aromatic-containing polymer with a sulfonation reagent in a batch or semi-batch reaction. Can be performed. In some other embodiments of the present technology, the sulfonation may be performed in a continuous reaction, such as, for example, a continuous stirred tank reactor or a series of two or more continuously stirred tank reactors. May be possible through the use of.

  As a result of the sulfonation, the micelle core includes an easily sulfonated block having a sulfonic acid functional part and / or a sulfonic acid ester functional part, and the micelle core is surrounded by an outer shell containing the sulfonated resistant block of the block copolymer. The driving force for this phase separation (causing the formation of micelles) in solution is due to the large difference in polarity between the sulfonated block (s) and unsulfonated block of the sulfonated block copolymer. The latter block can be freely solvated by a non-halogenated aliphatic solvent, such as the first solvent disclosed above. On the other hand, the sulfonated polymer block (s) can be centrally arranged in the core of the micelle.

  Once the sulfonation reaction is complete, the block copolymer can be cast directly into an article form (eg, a membrane) and it is not necessary to isolate the block copolymer. In this particular embodiment, a polymer membrane (eg, a membrane) may be immersed in water, and this form (solid) is retained in water. In other words, the block copolymer does not dissolve in water or is not dispersed in water.

(V) Additional Components In addition, the copolymer disclosed herein may be blended with other components that do not adversely affect the properties of the copolymer or the membrane formed from the sulfonated block copolymer.

Shape Retention Frame A shape retention frame may be used for the ERV core disclosed herein. Such a form may be, for example, one formed by heat or one formed by a machine (for example, a corrugation method). Such a frame can be a rigid or semi-rigid structure or sheet. Such a frame is capable of maintaining this form and shape (ie, mechanical strength) on its own without any other support. Preferably, the frame is in the form of a sheet and is made of fiberglass, aluminum or a hard polymer or a composite of such materials.

  The metal can include aluminum, copper, tin, nickel or steel, with aluminum being most preferred. The plastic used is not limited, but is thick enough to maintain a specific shape, sufficiently rigid and does not impede the passage of air flow, for example, polyethylene, polypropylene, polyvinyl chloride ( PVC), styrene / acrylonitrile / butadiene (ABS), Nomex® and Kevlar®. The sheet may be formed by extrusion, molding or sintering by conventional means and may be knitted or non-woven.

  Sheets can be in various forms, such as nets, screen meshes or grids, metal meshes, woven and non-woven metals or polymers, perforated or perforated plates. The piercing may be performed by puncturing the frame with a needle having a desired thickness as an example. The preferred frame is porous and rigid enough to maintain the preformed shape.

  For example, FIGS. 1a, 1b and 1c show three different extruded polymer mesh frames. Figures 2a, 2b, 2c show three different perforated aluminum plates.

  The frame is porous, and such pores are of sufficient size to allow direct air contact without hindering moisture transport or significant pressure drop. Depending on the material, the pores can be from submicron to 8 cm, or 10 cm, or more. For example, in a frame formed in a net, the pores or openings that make up the net can be from submicron to 5 cm, or from 0.1 to 4 cm, or from 1 to 3 cm. For perforated or perforated aluminum or plastic plates, the pores can be from submicron to 5 cm, or from 0.1 to 4 cm, or from 1 to 3 cm. In particular, the plate can have a larger frame surface area around the opening compared to a net that can be thin and have a thread-like surface between the pores. In any case, the surface of the frame between the pores should be sufficient to bond the polymer film and maintain adhesion.

  For non-woven or knitted frames (which can be metal or polymer), in some embodiments, the pore diameter is from 0.1 to 200 microns, or from 1 micron to 100, or 5 To 50 microns. For sintered frames, the pores can be from 0.01 to 200 microns, or from 0.1 microns to 100, or from 5 to 50 microns.

  The frame should be thick enough to maintain strength and not impede airflow or moisture transport. The thickness depends on many factors, such as the number of stacked layers of the frame, the speed and pressure of air flow, and the strength required to maintain the ERV core. Thus, the thickness can be from 25 microns to 500 microns, or from 100 microns to 500 microns, or from 200 microns to 500 microns.

  The shape, depth, degree of flexion and distribution of the pores can affect the air flow pattern inside the wind tunnel (eg, cause some turbulence), and in contact with the membrane joined to the frame Can also affect. The depth of the pores is generally determined by the thickness of the frame. Further, the pore shape can be a square, circular, spherical, hexagonal or other polygonal shape.

  The sulfonated block copolymer membrane disclosed herein can be joined to the frame by heat or adhesive lamination or coating. The bond should be such that a layer of polymer membrane exists so as to act as a barrier against the passage of air across the plurality of pores in the frame. Such polymer membranes may be continuous so that the entire frame is covered, or only filled in the pores. However, the pores in the frame allow the air flow to reach directly through the moisture permeable membrane.

  The rigid or semi-rigid frame may have a flat planar shape, or may be formed in a shape that functions as a spacer. When formed into a shape that serves as a spacer, the frame should be sufficiently rigid to maintain this configuration. However, while some flexibility may be tolerated, it should be limited to the extent that ERV core stability is maintained and significant pressure drops are avoided. In addition, when acting as a spacer, the frame is sufficient for continuous corrugation, corrugation, ridge shape, or air flow between the continuous surface of the membrane and other layers in the ERV core. It can have other shapes to maintain space. The frame can be heat, machined, or chemically formed into the desired shape.

Substrate The substrate is optionally used with a sulfonated polymer membrane to provide mechanical strength while allowing air flow and moisture transport. Therefore, it should be made of a porous material that allows humid air to pass with as little resistance as possible and also provides structural integrity. Porous substrates can be those known and used in the art, many of which are commercially available.

  As the substrate, the above-mentioned rigid or semi-rigid frame may be mentioned, and the substrate may have a low-rigidity flexibility such as a cellulosic paper material. Furthermore, the pores may be very small, for example microporous. Thus, the pores can be less than 10 microns, or less than 5 microns, or less than 2 microns, or less than 0.1 microns. However, one skilled in the art will understand that the pores should not be so small that air is too narrow to pass through the polymer membrane. Alternatively, a substrate having a large pore diameter may be used. For example, less than 5 cm, or less than 1 cm, or less than 1 mm, or less than 500 microns. Thus, the pores can have a range of 0.1 microns to 5 cm, or 2 microns to 1 cm, or 2 microns to 500 microns.

  Accordingly, the substrate used with the membrane disclosed in the present specification includes a porous cellulosic fibrous material. Examples of the material include fabrics, polymer films and fibers, and cellulosic materials (such as paper). The substrate may be composed of natural and / or synthetic fibers. Examples of the fabric include a knitted fabric, a non-woven fabric, a knit fabric, and a cloth fabric.

  FIG. 3 shows a nonwoven cellulosic substrate having pores less than 200 microns. Furthermore, a sintered porous substrate having pores of less than 100 microns is shown in FIG.

  Further, the substrate may be composed of filaments, glass yarns, fiber glass, corrosion-resistant metal fibers (such as nickel fibers), and carbon fibers. Synthetic fibers include polyolefin, polyethylene, polypropylene, polyester, nylon, Nomex (registered trademark) and Kevlar (registered trademark).

  Exemplary substrates include polyvinylidene fluoride, polytetrafluoroethylene, nylon, polyethersulfone, polypropylene, polyamide, cellulose, cellulose nitrate, cellulose acetate, cellulose nitrate / acetate polytetrafluoroethylene, polyethylene terephthalate ( PET) and polyetheretherketone (PEEK).

  Additives or coatings (other than sulfonated polymer coatings) may be added to the substrate to improve other properties. Such additives should not interfere with the effectiveness and efficiency of the ERV unit or introduce any harmful components into the air stream. One example of an additive type is a flame retardant, which can be used to prevent or suppress fire or fire spread. For example, non-halogen flame retardants can be used with phosphorus-containing compounds. Other useful flame retardants known in the art may be used.

  In addition, biocides such as fungicides, microbicides and fungicides can be harmful to mold, mildew, fungi, bacteria, viruses and parasites and humans, or otherwise reduce the efficiency of ERV units. It may be applied to suppress the growth of organisms.

  Other additives to improve moisture transport, such as silica, alumina and zeolites, may be added to the substrate to increase strength, porosity and lifetime.

Spacers Spacers can be used for the ERV cores described herein. The spacer is made of the same material as the rigid or semi-rigid frame, i.e. fiberglass, metal, plastic or a composite of such materials. In some embodiments, the metal used is aluminum, copper, tin, nickel or steel. Preferably, the spacer is an aluminum plate or a hard plastic.

  Spacers are known in the art and relate to providing a space for air flow between laminated polymer layers. Thus, the spacer can have a variety of shapes, with a corrugated or ridge shape being most preferred. In such a shape, a wind tunnel for the air flow is formed, and thus stacked in an alternating fashion that allows cross-flow patterns, or counter-current patterns, or cross-counter flow patterns to allow intake air flow and exhaust air flow to pass through. Can be done. Such a ridge or corrugated shape is shown, for example, in FIG. 2 of US Patent Publication No. 2012/0073791. Further, the wind tunnel may be straight or curved, and may have a zigzag pattern. A pattern with parallel curves is shown, for example, in US 2009/0314480.

  Further, such a spacer may also be porous and have a plurality of pores on the entire surface. Depending on the material, the pores can be from 0.1 microns to 5 cm. For example, in a frame formed in a net, the pores or openings that make up the net can be 0.05 cm to 5 cm, or 0.1 to 4 cm, or 1 to 3 cm. Such pores may be such that size, shape, depth, flexion, and distribution can effectively affect the air flow pattern, resulting in better contact between air and moisture permeable membranes or composites. Can be designed in any style.

  When the spacer is porous, in some embodiments, the sulfonated block copolymer membrane disclosed herein can be joined to the spacer by lamination, such as thermal lamination, adhesive lamination, as well as coating. The bond should be such that the layer of polymer membrane exists to function as a barrier to the passage of air through the plurality of pores of the spacer but to allow moisture transport.

  Thus, this thickness can be from submicron to 20 mm, or from 1 mm to 10 mm, or from 1 to 5 mm.

ERV Configuration The ERV core can have several configurations. An embodiment 1 of the ERV core unit is shown in FIG. As shown in the figure, the unit has a casing composed of a top cover 2, a bottom cover 3, and a side support 4. A laminated body of the structure 5 that is moisture permeable but not air permeable is held in the housing. The structure 5 can be multilayer and includes a sulfonated block copolymer membrane, a rigid or semi-rigid frame, a substrate and / or a spacer. In the illustrated embodiment, fresh intake air flow is indicated by arrow 8 and exhaust air flow is indicated by arrow B, so that the air flow has a cross-flow pattern.

  One embodiment of a moisture permeable but air impermeable structure 5 is shown in FIG. 6, with a sulfonated block copolymer membrane 6 and a spacer 7 sandwiched between the membranes. The spacer 7 is configured such that a channel for air flow is provided between the membranes 6. The size of such a channel 8 can be such that an air gap of about 2 to 30 mm is provided. In the embodiment shown in FIG. 6, this is done by forming the spacers 7 in a corrugated or ridge structure. The corrugated shape has a top 9 and a bottom 10 so that a longitudinal wind tunnel is formed in one direction along the length of the spacer, and therefore at both the top and bottom of the spacer depending on the structure of the ridge. Flow is allowed.

  The advantage of the configuration of FIG. 6 is that air passing through the wind tunnel 8 can contact the entire surface of the membrane 6 and can provide moisture transport throughout the membrane. In such embodiments, the sulfonated block copolymer membrane must have a thickness sufficient to support its own weight without the aid of additional substrates or structures to provide support. Accordingly, such membranes should have a thickness of 0.5 to 50, or 1 to 25, 1.5 to 13 microns.

  In FIG. 7 a, the frame 11 is a screen mesh and is separated from the sulfonated block copolymer membrane 6. When they are joined together, a multilayer structure is formed that functions as a barrier to air but assists moisture transport. The mesh is provided with pores through which air can pass without much obstruction to reach the membrane 6. In FIG. 7b, the membrane 6, the substrate 12 and the frame 11 are shown separated from one another. Even if they are joined together, a multilayer structure is formed that functions as a barrier to air but assists in moisture transport. The substrate 12 provides mechanical support for the membrane 6.

  Another embodiment is shown in FIG. 8a. In this case, the membrane 6 is bonded to the frame 11 of FIG. 7 a, thus forming a multilayer structure and then bonded to the spacer 7. As can be seen in the figure, this multilayer structure is joined to the top of the corrugated spacer 7 so that the wind tunnel 8 is maintained. The frame 11 may be bonded to one side or both sides of the membrane 6.

  As shown in FIG. 8b, the membrane 6 is joined to the base 12 and the rigid or semi-rigid frame 11 as shown in FIG. 7b to form a multilayer structure. This is then joined to the top of the corrugated spacer 7.

  9 shows the multilayer structure of FIG. 7b in which the membrane 6 is joined to the substrate 12 and a rigid or semi-rigid frame 11 and joined to the spacer 7. In the alternative embodiment shown in FIG. However, in the embodiment of FIG. 9, the corrugated spacer 14 is an aluminum screen mesh and is therefore porous. In another embodiment shown in FIG. 10 a, a sulfonated block copolymer membrane 15 is bonded to the spacer 14. In this embodiment, the membrane 15 is bonded to the entire surface of the spacer 14. Figures 10b and 10c show a further embodiment, in which multilayer structures such as those of Figures 3a and 3b, respectively, are joined. For example, in FIG. 10 b, the membrane 15 is bonded to the frame 16 to form a multilayer structure, which is then bonded to the entire surface of the spacer 14. The film 15 may be bonded to one side of the frame 16 or may be bonded to both sides. In FIG. 10 b, the membrane 15 is bonded to the substrate 17 and the frame 16 to form a multilayer structure, which is then bonded to the entire surface of the spacer 14. 10a to 10c, other embodiments include, in addition to the illustrated embodiment with all three layers, eg, membrane 15, substrate 17 and frame 16, only membrane 15 or membrane 15 and frame. 16 is joined to the spacer 14.

  In a further embodiment, such as that shown in FIG. 11a, the rigid or semi-rigid frame 18 may be an aluminum screen mesh formed in a corrugated shape and laminated with a sulfonated block copolymer membrane 19 on the top surface. In other embodiments, the screen mesh can be a plastic mesh. In either case, the frame 18 is sufficiently rigid to maintain this corrugation. Thus, a rigid or semi-rigid structure can also function as a spacer and as a membrane that can transport water but serve as a barrier to air flow. In the embodiment of FIG. 11 b, the membrane 18 can be first bonded to the substrate 20 and then bonded to the structure 18.

HRV to ERV Conversion The multilayer structure of FIGS. 11a and 11b can also be used to convert an HRV system to an ERV system. Existing plate-type HRVs are typically made of metal (eg, aluminum), plastic (eg, polypropylene) or paper and are configured for sensible heat recovery only. In an HRV system having a cross-flow pattern and a stack of corrugated plates or spaced plates, such a plate can be removed, after which the corrugated multilayer structure of FIGS. 11a and 11b with a rigid or semi-rigid frame is inserted. Thus, an ERV core can be formed. Due to the rigid or semi-rigid nature of the frame, the multi-layer composite can be flat and folded at the edges, or can be shaped to allow the passage of air. The edges can be sealed, for example, by alternately folding or crimping two edges of adjacent layers so that the air flow is separated (FIGS. 12a and 12b).

  For example, the HRV system of some embodiments is the same as the core of FIG. 5, but without a moisture transport layer, instead there are spacers stacked in an alternating fashion. Thus, when a sulfonated block copolymer laminate frame disclosed herein (a multilayer structure such as that of FIGS. 11a and 11b) is formed in the same shape as the layer of the HRV core, such layer is removed from the HRV core; A multilayer structure can be inserted to form the ERV core. No additional spacer can be required.

Lamination Lamination can be performed as is known in the art. In general, sulfonated block copolymers are formed into membranes, optionally using other components (hereinafter “polymer membranes”), and the porous substrates or rigid / semi-solids disclosed herein. Integrated with rigid structure or spacer. Many methods can be used for laminating a polymer film to attach or bond the polymer film to a porous substrate. For example, laminating can be done by cold laminating or heat laminating. Furthermore, ultrasonic bonding may be used for laminating.

  Thermal laminating is performed by bringing a polymer film into contact with a substrate or structure under temperature and pressure, thereby forming a bond therebetween. Lamination can be done in a bath, such as a furnace, or other machine or device that can press the polymer membrane and the porous substrate together. Generally, the temperature can range from 95 ° to 450 ° F. and the pressure can range from 100 to 7,000 psi. The residence time or time subjected to high temperature and pressure can be from 30 seconds to 10 minutes. The membrane can then be cooled at room temperature and room pressure to produce the final membrane. Various types of laminating assemblies known in the art can be used to contact the polymer film and the substrate under heat and pressure. Further, an adhesive may be used in the heat laminating process. In addition, heat activated adhesives may be used.

  A commercially available laminator is used as an example of a heat laminating mold. A laminator can have two or more nip rollers, where each roller can be controlled in temperature and pressure. The membrane of the sulfonated block copolymer disclosed herein is disposed on one substrate or structure, or between multiple layers of the substrate or structure, and then disposed between nip rollers, and thus two layers. Alternatively, a multilayer membrane can be formed. Typical operating conditions can include a temperature of 150 to 450 ° F., a pressure of 100 to 7000 psi, and the residence time can be adjusted by adjusting the line speed. Temperature, pressure and residence time can be varied to obtain the desired laminate joint.

  A further method of laminating is called solvent bonding. This can be done under heating or at room temperature. In this type of lamination, an organic solvent is applied to the sulfonated block copolymer membrane. Accordingly, the portion of the sulfonated polymer membrane that comes into contact with the solvent is softened. The membrane is then pressed onto the substrate, thereby forming a bond between the portion softened by the organic solvent and the substrate. An organic solvent having the effect of solvating a part of the polymer film can be used. Such organic solvents include alcohols, alkyls, ketones, acetates, ethers, and aromatic solvents such as toluene and benzene.

  Another method for laminating is cold laminating, which typically uses wet or dry adhesives. Although indicated as cold, such temperatures include room temperature. Adhesive laminating is performed by applying an adhesive to one side of the polymer film and then contacting it with a porous substrate. However, the adhesive should be applied so that a specific surface area of the substrate and polymer film is covered so that there is minimal blockage that may prevent the passage of vapors. The adhesive may have an effect of blocking a part of the pores of the base material, which may reduce the efficiency. Therefore, in the adhesive laminating process, it is preferable to minimize the area covered with the adhesive. The adhesive used can be, for example, urethane or latex.

  Also, in either case of cold or thermal laminating, a laboratory or commercial scale laminating assembly can be used to contact and join the polymer film and the substrate to form a laminate. There are many possible configurations for commercial scale laminating, such as rollers, presses, and the most popular in the art is the use of dual heated pinch rollers.

  When the polymer membrane is contacted with the porous substrate, measures can be taken to ensure that the membrane is flat with respect to the porous substrate. For example, a laminating device with a roller can be applied to the entire surface to flatten and remove bubbles.

  The following examples are intended to be illustrative only and are not intended to limit the scope of the invention in any way and should not be construed as limiting.

a. Materials and Methods Degree of sulfonation: The degree of sulfonation described herein and measured by titration was measured by the following potentiometric titration procedure. The solution of the sulfonation reaction product was analyzed by two separate titrations (“phase separation titration method”), and the sulfonic acid, sulfuric acid of the styrenic polymer, and the sulfonic acid (2-sulfoisobutyric acid) level of the non-polymer by-product Was measured. For each titration, approximately 5 grams aliquots of the reaction product solution were dissolved in approximately 100 mL of tetrahydrofuran and approximately 2 mL of water and approximately 2 mL of methanol were added. In the first titration, the solution was titrated by potentiometric titration with 0.1N cyclohexylamine in methanol to obtain two endpoints. The first end point corresponded to the total sulfonic acid groups in the sample plus the first acidic proton of sulfuric acid, and the second end point corresponded to the second acidic proton of sulfuric acid. In the second titration, the solution was titrated by potentiometric titration with 0.14N sodium hydroxide in about 3.5: 1 methanol: water to give three endpoints. The first endpoint corresponds to the total sulfonic acid groups in the sample plus the first and second acidic protons of sulfuric acid, the second endpoint corresponds to the carboxylic acid of 2-sulfoisobutyric acid, and the third endpoint corresponds to isobutyric acid. .

  When the selective detection of the second acidic proton of sulfuric acid in the first titration was combined with the selective detection of the carboxylic acid of 2-sulfoisobutyric acid in the second titration, it was possible to calculate the concentration of the acid component.

The degree of sulfonation described herein and measured by 1H-NMR was measured using the following procedure. About 2 grams of the solution of non-neutralized sulfonated polymer product was treated with a few drops of methanol and the solvent was stripped off by drying in a vacuum oven at 50 ° C. for approximately 0.5 hours. A 30 mg sample of the dried polymer was dissolved in about 0.75 mL of tetrahydrofuran-d ₈ (THF-d ₈ ), and then less than 1 drop of concentrated H ₂ SO ₄ was added to it to prevent interference. The stable proton signal was shifted to the low magnetic field side of the aromatic proton signal in the subsequent NMR analysis. The obtained solution was analyzed at about 60 ° C. by ¹ H-NMR. The percentage of styrene sulfonation is the ¹ H-NMR signal at about 7.6 parts per million (ppm), which corresponds to half of the aromatic protons of the sulfonated styrene unit, which corresponds to the other half of such aromatic protons. Signal was calculated by integrating the signal corresponding to the unsulfonated styrene aromatic proton and the signal corresponding to the tert-butylstyrene aromatic proton).

  The ion exchange capacities described herein were measured by the potentiometric titration method described above and reported as milliequivalents of sulfonic acid functionality per gram of sulfonated block copolymer.

b. Experimental Preparation of Sulfonated Block Copolymer SBC-1 A pentablock copolymer having the configuration A-D-B-D-A was prepared by sequential anionic polymerization. Here, the A block is a polymer block of para-tert-butylstyrene (ptBS), the D block is composed of a polymer block of hydrogenated isoprene (Ip), and the B block is a polymer block of unsubstituted styrene (S). Configured. Anionic polymerization of t-butylstyrene in cyclohexane was initiated using sec-butyllithium to obtain an A block having a molecular weight of 15,000 g / mol. Next, isoprene monomer was added to obtain a second block (ptBS-Ip-Li) having a molecular weight of 9,000 g / mol. Subsequently, a styrene monomer was added to the living (ptBS-Ip-Li) diblock copolymer solution and polymerized to obtain a living triblock copolymer (ptBS-Ip-S-Li). The styrene block of the polymer consisted solely of polystyrene having a molecular weight of 28,000 g / mol. To this solution, a further aliquot of isoprene monomer was added to obtain an isoprene block having a molecular weight of 11,000 g / mol. Therefore, this gave a living tetrablock copolymer structure (ptBS-Ip-S-Ip-Li). A second aliquot of para-tertbutylstyrene monomer was added and the polymerization was terminated by the addition of methanol, resulting in a ptBS block having a molecular weight of about 14,000 g / mol. The ptBS-Ip-S-Ip-ptBS was then hydrogenated using a standard Co ²⁺ / triethylaluminum method to remove C═C unsaturation in the isoprene portion of the pentablock. The block polymer was then sulfonated directly (no further treatment, oxidation, no washing, no “finishing”) using ibutyric anhydride / sulfuric acid reagent. The hydrogenated block copolymer solution was diluted to about 10% solids by the addition of heptane (approximately the same volume of heptane relative to the volume of the block copolymer solution). Sufficient i-butyric anhydride and sulfuric acid (1/1 (mol / mol)) were added to obtain a sulfonated polystyrene functional part of 2.0 meq per 1 g of block copolymer. The sulfonation reaction was terminated by the addition of ethanol (2 mol ethanol / mol i-butyric anhydride). The resulting polymer was shown by potentiometric titration to have an “ion exchange capacity (IEC)” of 2.0 meq of —SO ₃ H / g polymer. The sulfonated polymer solution had a solids level of about 10% weight / weight in a mixture of heptane, cyclohexane and ethyl i-butyrate.

  For use of a cast membrane, the above composition was cast onto a release liner such as a silicone treated PET membrane. The membrane was slowly dried in an oven (controlled temperature in the zone and air or nitrogen purge) for at least 2 minutes until the desired residual solvent level was reached. Except as specifically required for specific test procedures, the membrane was not further post-treated. Typical film thicknesses obtained by this procedure range from 5 microns to 50 microns. SBC-1 was cast according to this method and formed into a film.

  Table 1 shows a comparison between a typical HRV system and an ERV system in which the multilayer structure of the present disclosure was used. In particular, the HRV system of Comparative Example No. 1 uses an aluminum barrier (ie, a spacer) and does not use a polymer membrane or other moisture transport material. Therefore, only sensible heat is used.

In ERV system number 2, a corrugated aluminum spacer plate is used with a mesh screen mesh wrapper as a semi-rigid structure, which wrapper has an SBC-1 membrane laminated on its top surface. SBC-1 was hot laminated in the press at temperatures in the range of 280 to 350 ^° F., pressures of 60 to 5000 psi, and heating times of approximately a few seconds to 2 minutes. In this embodiment, the spacer is not porous and does not allow the passage of air or moisture.

  In ERV system number 2, the spacer used is a corrugated screen mesh wrapper, and the SBC-1 film is heat laminated. Also, the screen mesh is used as a semi-rigid structure, and the SBC-1 film is heat laminated. Thermal lamination was performed under the same conditions as in ERV Example No. 3.

  The sensible heat and latent heat values were tested according to the American Air Conditioning Heating and Refrigerating Industry Association (AHRI) Standard 1060.

上記の表からわかるように、コートスクリーンラッパーを有するＥＲＶ実施例番号２では、顕熱および潜熱の回収効率が比較例番号１のＨＲＶシステムよりもずっと高い。さらに、実施例番号３に示されるように、波形ＳＢＣ−１コートスクリーンスペーサーを使用すると、顕熱と潜熱の両方の効率が驚くほど有意に増大している。結果を図１３にグラフの形態で示す。

As can be seen from the above table, ERV Example No. 2 with a coated screen wrapper has much higher sensible and latent heat recovery efficiency than the HRV system of Comparative Example No. 1. Further, as shown in Example No. 3, the use of a corrugated SBC-1 coated screen spacer has surprisingly significantly increased both sensible and latent heat efficiencies. The results are shown in the form of a graph in FIG.

Claims (4)

An energy recovery system having a core unit that allows the exchange of heat and moisture between the air flow passing through the interior, the core unit includes a two or more multi-layer composite structure, the multilayered composite structure Is
A porous rigid or semi-rigid frame having a plurality of holes leading from the first surface to the second surface; and the plurality of holes joined to at least one of the first and second surfaces of the frame the first polymer film comprising a sulfonated block copolymer covering the,
A plurality of corrugated spacer plates having channels formed on a surface, the channels having a top and bottom corrugated spacer plate; and
A second polymer membrane comprising a sulfonated block copolymer bonded to the surface of the corrugated spacer plate including the top and bottom of the channel;
With
The sulfonated block copolymer has at least one end block A and at least one internal block B, wherein each A block contains essentially sulfonic acid functional groups or sulfonic acid ester functional groups. Orazu, each B block is a polymer block der containing from about 10 to about 100 mole percent of the sulfonic acid functional group or a sulfonic acid ester functional group relative to the number of monomer units is,
Each of the plurality of multilayer composite structures is fixed on each surface of the plurality of corrugated spacer plates,
A space exists in the channel between the second polymer membrane and the plurality of multilayer composite structures secured to the second polymer membrane;
Energy recovery system. A porous rigid or semi-rigid frame having a plurality of holes leading from a first surface to a second surface , wherein the frame is formed into a shape having a channel formed on the surface, wherein the channel A first polymer membrane comprising a sulfonated block copolymer joined to at least one of the first and second surfaces of the frame and covering the plurality of holes ;
A plurality of corrugated spacer plates having channels formed on a surface, the channels having a top and bottom corrugated spacer plate; and
A second polymer membrane comprising a sulfonated block copolymer bonded to the surface of the corrugated spacer plate including the top and bottom of the channel ;
The sulfonated block copolymer has at least one end block A and at least one internal block B, wherein each A block contains essentially sulfonic acid functional groups or sulfonic acid ester functional groups. Each B block is a polymer block containing from about 10 to about 100 mole percent sulfonic acid functional groups or sulfonic acid ester functional groups based on the number of monomer units, a multilayer for latent heat and sensible heat exchange Composite structure. An energy recovery system having a core unit that allows heat and moisture exchange between air streams passing through the interior,
A corrugated spacer plate having a channel formed in the surface, the channel having a top and a bottom;
A substantially planar membrane comprising a sulfonated block copolymer joined to the top of the channel to form a space for air flow between the membrane and the bottom of the channel ; and
A second polymer film comprising a sulfonated block copolymer bonded to the surface of the channel of the corrugated spacer plate including the top and bottom, between the second polymer film and the substantially planar film A second polymer film in which a space for air flow is formed;
With
The sulfonated block copolymer has at least one end block A and at least one internal block B, wherein each A block contains essentially sulfonic acid functional groups or sulfonic acid ester functional groups. Each B block is a polymer block containing from about 10 to about 100 mole percent sulfonic acid functional groups or sulfonic acid ester functional groups based on the number of monomer units.
Energy recovery system. Removing the spacer plate from the core of the heat recovery ventilator,
A method for converting a heat recovery ventilation system to an energy recovery system comprising inserting a multilayer structure, the multilayer structure comprising:
A porous rigid or semi-rigid frame having a plurality of molded holes extending from the first surface to the second surface; and joined to at least one of the first and second surfaces of the frame A first polymer membrane comprising a sulfonated block copolymer covering a plurality of holes ;
A plurality of corrugated spacer plates having channels formed on a surface, the channels having a top and bottom for allowing air flow therein; and
A second polymer membrane comprising a sulfonated block copolymer joined to the surface of the corrugated spacer plate including the top and bottom of the channel ;
The sulfonated block copolymer has at least one end block A and at least one internal block B, wherein each A block contains essentially sulfonic acid functional groups or sulfonic acid ester functional groups. Each B block is a polymer block containing from about 10 to about 100 mole percent sulfonic acid functional groups or sulfonic acid ester functional groups based on the number of monomer units ;
Each of the plurality of multilayer composite structures is fixed on each surface of the plurality of corrugated spacer plates,
A space exists in the channel between the second polymer membrane and the plurality of multilayer composite structures secured to the second polymer membrane;
Method.

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